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Facile H/D Exchange at (Hetero)Aromatic Hydrocarbons Catalyzed by a Stable Trans-Dihydride N-Heterocyclic Carbene (NHC) Iron Complex
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-09-09 , DOI: 10.1021/jacs.0c07689
Subhash Garhwal 1 , Alexander Kaushansky 1 , Natalia Fridman 1 , Linda J W Shimon 2 , Graham de Ruiter 1
Affiliation  

Earth-abundant metal pincer complexes have played an important role in homogeneous catalysis during the last ten years. Yet, despite intense research efforts, the synthesis of iron PCcarbeneP pincer complexes has so far remained elusive. Here we report the synthesis of the first PCNHCP functionalized iron complex [(PCNHCP)FeCl2] (1) and the reactivity of the corresponding trans-dihydride iron(II) dinitrogen complex [(PCNHCP)Fe(H)2N2)] (2). Complex 2 is stable under an atmosphere of N2 and is highly active for hydrogen isotope exchange at (hetero)aromatic hydrocarbons under mild conditions (50 °C, N2). With benzene-d6 as the deuterium source, easily reducible functional groups such as esters and amides are well tolerated, contributing to the overall wide substrate scope (e.g., halides, ethers, and amines). DFT studies suggest a complex assisted σ-bond metathesis pathway for C(sp2)–H bond activation, which is further discussed in this study.

中文翻译:

由稳定的反式二氢化物 N-杂环卡宾 (NHC) 铁配合物催化的(杂)芳烃的 H/D 交换

在过去的十年中,地球上丰富的金属钳形配合物在均相催化中发挥了重要作用。然而,尽管进行了大量研究,但迄今为止,铁 PCcarbeneP 钳形复合物的合成仍然难以捉摸。在这里,我们报告了第一个 PCNHCP 功能化铁络合物 [(PCNHCP)FeCl2] (1) 的合成以及相应的反式二氢化铁 (II) 二氮络合物 [(PCNHCP)Fe(H)2N2)] (2) . 配合物 2 在 N2 气氛下是稳定的,并且在温和条件(50 °C,N2)下(杂)芳烃的氢同位素交换具有高活性。以苯-d6 作为氘源,容易还原的官能团(如酯和酰胺)具有良好的耐受性,有助于整体广泛的底物范围(例如卤化物、醚和胺)。
更新日期:2020-09-09
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